Phase change inks containing colorant compounds

ABSTRACT

Disclosed is a phase change ink composition comprising a phase change ink carrier and a compound of the formula 
     
       
         
         
             
             
         
       
     
     and dimers thereof, wherein R, R 2 , X and Z are as described herein.

Cross-reference is made to the following co-pending applications:

Co-pending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20060164-US-NP), filed concurrently herewith, entitled “ColorantCompounds,” with the named inventor Jeffery H. Banning, et al., thedisclosure of which is totally incorporated herein by reference,discloses a colorant compound of the formula

and dimers thereof.

Co-pending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20060165-US-NP), filed concurrently herewith, entitled “ColorantCompounds,” with the named inventors Jeffery H. Banning, et al., thedisclosure of which is totally incorporated herein by reference,discloses compounds of the formula

and dimers thereof.

Co-pending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20060165Q-US-NP), filed concurrently herewith, entitled “PhaseChange Inks Containing Colorant Compounds,” with the named inventorsJeffery II. Banning, et al., the disclosure of which is totallyincorporated herein by reference, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound.

BACKGROUND

The present disclosure is generally related to phase change inks. Morespecifically, the present disclosure is directed to hot melt or phasechange inks containing specific colorant compounds. In embodiments, thepresent disclosure is directed to hot melt or phase change inkscontaining dimeric azo acetoacetamido colorant compounds. One embodimentof the present disclosure is directed to a phase change ink compositioncomprising a phase change ink carrier and a colorant compound of theformula

and dimers thereof, wherein R is an N-substituted acetoacetamide; R₂ is(i) an alkyl group, (ii) an alkylene group, (iii) an arylene group, (iv)an arylalkylene group, (v) an alkylarylene group, (vi) an alkyleneoxygroup, (vii) an aryleneoxy group, (viii) an arylalkyleneoxy group, (ix)an alkylaryleneoxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a heterocyclic group, (xv) a silylenegroup, (xvi) a siloxane group, (xvii) a polysilylene group, or (xiii) apolysiloxane group; X is a (i) direct bond, (ii) an oxygen atom, (iii) anitrogen atom, (iv) a sulfur atom, (v) a group of the formula —NR₄₀—wherein R₄₀ is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, or an alkylaryl group, (vi) or a group of the formula—CR₅₀R₆₀—; wherein R₅₀ and R₆₀ each, independently of the other, is ahydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group; and Z is optionally present and if present is a (i)hydrogen atom, (ii) a halogen atom, (iii) a nitro group, (iv) an alkylgroup, (v) an aryl group, (vi) an arylalkyl group, (vii) an alkylarylgroup, (viii) a group of the formula

wherein R₁₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, an alkoxy group, an aryloxy group, an arylalkyloxygroup, an alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxygroup, a heterocyclic group, a silyl group, a siloxane group, apolysilylene group, or a polysiloxane group, (ix) a sulfonyl group ofthe formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, anaryl group, an arylalkyl group, an alkylaryl group, an alkoxy group, anaryloxy group, an arylalkyloxy group, an alkylaryloxy group, apolyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxygroup, a polyalkylaryleneoxy group, a heterocyclic group, a silyl group,a siloxane group, a polysilylene group, or a polysiloxane group, or (x)a phosphoryl group of the formula —PO₃R₉₀ wherein R₉₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, an alkylarylgroup, an alkoxy group, an aryloxy group, an arylalkyloxy group, analkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, apolyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclicgroup, a silyl group, a siloxane group, a polysilylene group, or apolysiloxane group.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclose of which is totally incorporated herein by reference. U.S. Pat.No. 5,621,022, the disclosure of which is totally incorporated herein byreference, discloses the use of a specific class of polymeric dyes inphase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labeling. Phase change inks aredesirable for ink jet printers because they remain in a solid phase atroom temperature during shipping, long term storage, and the like. Inaddition, the problems associated with nozzle clogging as a result ofink evaporation with liquid ink jet inks are largely eliminated, therebyimproving the reliability of the ink jet printing. Further, in phasechange ink jet printers wherein the ink droplets are applied directlyonto the final recording substrate (for example, paper, transparencymaterial, and the like), the droplets solidify immediately upon contactwith the substrate, so that migration of ink along the printing mediumis prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,576,747 of Rina Carlini et al., entitled “Processes forPreparing Dianthranilate Compounds and Diazopyridone Colorants,” whichis hereby incorporated by reference herein in its entirety, discloses aprocess for preparing dianthranilate compounds which comprises (a)admixing reactants as follows: (1) a diol of the formula R1(OH)2,wherein R1 is an alkylene group having at least about 20 carbon atoms,and wherein the —OH groups are primary or secondary, (2) isatoicanhydride, present in an amount of at least about 2 moles of isatoicanhydride per every one mole of diol, (3) a catalyst which is1,4-diazabicyclo[2,2,2]octane, N,N,N′,N′-tetramethylethylene diamine, ora mixture thereof, said catalyst being present in an amount of at leastabout 0.2 mole of catalyst per every one mole of diol, and (4) asolvent; and (b) heating the mixture thus formed to form adianthranilate compound of the formula

Also disclosed is a process for preparing diazopyridone colorants whichcomprises (1) preparing a dianthranilate compound by the aforementionedmethod, (II) reacting the dianthranilate compound with nitrosylsulfuricacid to form a diazonium salt and (III) reacting the diazonium salt witha pyridine compound to form a diazopyridone compound.

U.S. Pat. No. 6,713,614 of Rina Carlini et al., entitled “Dimeric AzoPyridone Colorants,” which is hereby incorporated by reference herein inits entirety, discloses compounds of the formula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,663,703 of Bo Wu et al., entitled “Phase Change InksContaining Dimeric Azo Pyridone Colorants,” which is hereby incorporatedby reference herein in its entirety, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

U.S. Pat. No. 6,755,902 Patent of Jeffrey H. Banning et al. entitled“Phase Change Inks Containing Azo Pyridone Colorants” which is herebyincorporated by reference herein in its entirety, discloses a phasechange ink composition comprising a phase change ink carrier and acolorant compound of the formula

U.S. Pat. No. 6,590,082 of Jeffrey H. Banning et al. entitled “AzoPyridone Colorants,” which is hereby incorporated by reference herein inits entirety, discloses compounds of the formula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,696,552 of James D. Mayo et al. entitled “Process forPreparing Substituted Pyridone Compounds,” which is hereby incorporatedby reference herein in its entirety, discloses a process for preparingsubstituted pyridone compounds which comprises (a) admixing in theabsence of a solvent (1) an amine of the formula R1-NH₂ wherein R1 is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and (2) a first ester of the formula

wherein R₂ is an electron withdrawing group and R₃ is an alkyl group;(b) heating the mixture containing the amine and the first ester to forman intermediate compound of the formula

(c) admixing the intermediate compound with (1) a base and (2) a secondester of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group and R₅ is an alkyl group, said second ester beingpresent in a molar excess relative to the intermediate compound, saidbase being present in a molar excess relative to the intermediatecompound, and (d) heating the mixture containing the intermediatecompound, the second ester, and the base to form a pyridone compound ofthe formula

or a salt thereof. Also disclosed is a process for preparingdiazopyridone colorants which comprises preparing a pyridone compound bythe above process and reacting the pyridone compound with a diazoniumsalt to form a diazopyridone compound.

U.S. Pat. No. 6,576,748 of Rina Carlini et al. entitled “Method forMaking Dimeric Azo Pyridone Colorants,” which is hereby incorporated byreference herein in its entirety, discloses a process for preparing adiazopyridone compound which comprises (a) preparing a first solutioncomprising (1) either (A) a dianiline of the formula

or (B) an aniline of the formula

and (2) a first solvent mixture comprising (I) a solvent, (II) aceticacid, and (III) an optional second acid, said acetic acid being presentin the solvent mixture in an amount of at least about 95 percent byweight of the solvent mixture, said first solution being at atemperature of about +15° C. or lower; (b) adding to the first solutionnitrosylsulfuric acid, thereby forming a diazonium salt either (A) ofthe formula

or (B) of the formula

(c) preparing a second solution comprising (1) a second solvent mixturecomprising water and an organic solvent soluble in or miscible in water,(2) either (A) a pyridone of the formula

or (B) a dipyridone of the formula

(3) a base present in an amount of at least about 3 molar equivalents ofbase per mole of pyridone moiety, and (4) an optional buffer salt, and(d) combining either (A) the second solution containing the dianilineand the first solution containing the pyridone, or (B) the secondsolution containing the aniline and the first solution containing thedipyridone to form a third solution and effect a coupling reaction toform a diazopyridone compound either (A) of the formula

or (B) of the formula

U.S. Pat. No. 6,646,111 of Rina Carlini et al. entitled “Dimeric AzoPyridone Colorants,” which is hereby incorporated by reference herein inits entirety, discloses compounds of the formula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,673,139 of Bo Wu et al. entitled “Phase Change InksContaining Dimeric Azo Pyridone Colorants,” which is hereby incorporatedby reference herein in its entirety, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

While known compositions and processes are suitable for their intendedpurposes, a need remains for new colorant compositions, for example newyellow to orange colorant compositions. In addition, a need remains foryellow to orange colorant compositions particularly suitable for use inphase change inks. Further, a need remains for yellow to orangecolorants with desirable thermal stability. Additionally, a need remainsfor yellow to orange colorants that exhibit minimal undesirablediscoloration when exposed to elevated temperatures. There is also aneed for yellow to orange colorants that exhibit a desirable brilliance.In addition, there is a need for yellow to orange colorants that exhibita desirable hue. Further, there is a need for yellow to orange colorantsthat are of desirable chroma. Additionally, there is a need for yellowto orange colorants that have desirably high lightfastnesscharacteristics. A need also remains for yellow to orange colorants thathave a desirably pleasing color. In addition, a need remains for yellowto orange colorants that exhibit desirable solubility characteristics inphase change ink carrier compositions. Further, a need remains foryellow to orange colorants that enable phase change inks to be jetted attemperatures of over 135° C. while maintaining thermal stability.Further, a need remains for yellow to orange colorants for use in solidink printers that operate with lower print head temperatures much lowerthan 135° C. as well as in ultraviolet radiation curable systems.Additionally, a need remains for yellow to orange colorants that enablephase change inks that generate images with low pile height. There isalso a need for yellow to orange colorants that enable phase change inksthat generate images that approach lithographic thin image quality. Inaddition, there is a need for yellow to orange colorants that exhibitoxidative stability. Further, there is a need for yellow to orangecolorants that do not precipitate from phase change ink carriers.Additionally, there is a need for yellow to orange colorants that donot, when included in phase change inks, diffuse into adjacently printedinks of different colors. A need also remains for yellow to orangecolorants that do not leach from media such as phase change ink carriersinto tape adhesives, paper, or the like. In addition, a need remains foryellow to orange colorants that, when incorporated into phase changeinks, do not lead to clogging of a phase change ink jet printhead.Further; there is a need for yellow to orange colorants that enablephase change inks that generate images with sharp edges that remainsharp over time. Additionally, there is a need for yellow to orangecolorants that enable phase change inks that generate images whichretain their high image quality in warm climates. Further, there is aneed for yellow to orange colorants that enable phase change inks thatgenerate images of desirably high optical density. Additionally, thereis a need for yellow to orange colorants that, because of their goodsolubility in phase ink carriers, enable the generation of images of lowpile height without the loss of desirably high optical density. A needalso remains for yellow to orange colorants that enable cost-effectiveinks. The appropriate components and process aspects of the each of theforegoing may be selected for the present disclosure in embodimentsthereof.

SUMMARY

In embodiments, the present disclosure is directed to a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

and dimers thereof, wherein R is an N-substituted acetoacetamide;

R₂ is (i) an alkyl group, (ii) an alkylene group, (iii) an arylenegroup, (iv) an arylalkylene group, (v) an alkylarylene group, (vi) analkyleneoxy group, (vii) an aryleneoxy group, (viii) an arylalkyleneoxygroup, (ix) an alkylaryleneoxy group, (x) a polyalkyleneoxy group, (xi)a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a heterocyclic group, (xv) a silylenegroup, (xvi) a siloxane group, (xvii) a polysilylene group, or (xviii) apolysiloxane group;

X and X′, if X′ is present, is a (i) direct bond, (ii) an oxygen atom,(iii) a nitrogen atom, (iv) a sulfur atom, (v) a group of the formula—NR₄₀— wherein R₄₀ is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, or an alkylaryl group, (vi) or a group of the formula—CR₅₀R₆₀—; wherein R₅₀ and R₆₀ each, independently of the other, is ahydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, wherein two or more substituents can be joined togetherto form a ring and wherein X and X′ can be the same as each other ordifferent from each other; and

Z and Z′ are each optionally present and if present are eachindependently selected from a (i) hydrogen atom, (ii) a halogen atom,(iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi) anarylalkyl group, (vii) an alkylaryl group, (viii) a group of the formula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, an alkoxy group, an aryloxy group, an arylalkyloxygroup an alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxygroup, a heterocyclic group, a silyl group, a siloxane group, apolysilylene group, or a polysiloxane group, (ix) a sulfonyl group ofthe formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, anaryl group, an arylalkyl group, an alkylaryl group, an alkoxy group, anaryloxy group, an arylalkyloxy group, an alkylaryloxy group, apolyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxygroup, a polyalkylaryleneoxy group, a heterocyclic group, a silyl group,a siloxane group, a polysilylene group, or a polysiloxane group, or (x)a phosphoryl group of the formula —PO₃R₉₀ wherein R₉₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, an alkylarylgroup, an alkoxy group, an aryloxy group, an arylalkyloxy group, analkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, apolyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclicgroup, a silyl group, a siloxane group, a polysilylene group, or apolysiloxane group, wherein two or more substituents can be joinedtogether to form a ring, wherein Z and Z′ can be the same as each otheror different from each other; and wherein Z and X can be joined togetherto form a ring and wherein Z′ and X′ can be joined together to form aring.

In embodiments, the present disclosure includes dimeric compounds of theformula

wherein R, R₁, R₂, X, X′, Z and Z′ are as described herein.

DETAILED DESCRIPTION

The present disclosure is directed to phase change inks containingcolorant compounds as disclosed herein. In embodiments, the presentdisclosure is directed to phase change inks containing dimeric azoacetoacetamido colorant compounds. One embodiment of the presentdisclosure is directed to phase change inks containing colorantcompounds and dimerized colorant compounds of the formula

While not wishing to be bound by theory, as with pyrazolone andazopyridone dyes, it is noted that acetoacetamido dyes existpredominantly in the hydrazone form after synthesis. That is,acetoacetamido dyes initially form the enol (referred to as the diazoform) when the coupling reaction takes place and then tautomerize to theketo form (referred to as the hydrazone form). However, as withpyrazolone and azopyridone dyes, the acetoacetamido compounds can existin both forms. For example, under certain environmental conditions (forexample, in certain solvents), the acetoacetamido dye can revert back tothe diazo form.

The compounds can be dimerized through R or R′. For example, inembodiments, dimers of the keto form (hydrazone form)

include

For example, in embodiments, dimers of the enol form (diazo form)

include

wherein R and R′, if R′ is present, is an N-substituted acetoacetamide;for example, in embodiments, R and R′ is, for example,2-ethylhexylacetoacetamide, dodecylanilineacetoacetamide,Guerbet-acetoacetamide, or p-hydroxyethylanilino-acetoacetamide, and thelike.

A Guerbet alcohol refers to a beta-branched primary alcohol of thegeneral formula

wherein R₁₀ and R₁₁ each, independently of the other, are alkyl groups(including linear, branched, saturated, unsaturated, cyclic, andsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like, either mayor ma not be present in the alkyl group), typically with from about 1 toabout 22 carbon atoms; or about 1 to about 12 carbon atoms, or about 1to about 7 carbon atoms, although the number of carbon atoms can beoutside of these ranges, aryl groups (including substituted arylgroups), typically with from about 6 to about 30 carbon atoms, or fromabout 6 to about 15 carbon atoms, or from about 6 to about 12 carbonatoms, although the number of carbon atoms can be outside of theserangers, arylalkyl groups (including substituted arylalkyl groups),typically with from about 7 to about 30 carbon atoms, or from about 7 toabout 15 carbon atoms, or from about 7 to about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, alkylaryl groups (including substituted alkylarylgroups), typically with from about 7 to about 30 carbon atoms, or fromabout 7 to about 15 carbon atoms, or from about 7 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, alkoxy groups (including substituted alkoxy groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphoris,boron, and the like can be present in the alkoxy group), typically withfrom about 1 to about 22 carbons, or from about 1 to about 12 carbonsatoms, or from about 1 to about 7 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, polyalkyleneoxy groups(including substituted polyalkyleneoxy groups), such as polyethyleneoxygroups, polypropyleneoxy groups, polybutyleneoxy groups, and the like,typically with from about 3 to about 60 repeat alkyleneoxy units, orfrom about 3 to about 30 repeat alkyleneoxy units, or from about 3 toabout 20 repeat alkyleneoxy units, although the number of repeatalkyleneoxy units can be outside of these ranges, although the number ofrepeat alkyleneoxy units can be outside of these ranges, wherein R₁₀ andR₁₁ can be joined together to form a ring, and wherein the substituentson the substituted alkyl, aryl, arylalkyl, alkylaryl, alkoxy, andpolyalkyleneoxy groups can be, but are not limited to, hydroxy groups,amine groups, ammonium groups, pyridine groups, pyridinium groups, ethergroups, ester groups, amide groups, carbonyl groups, mixtures thereof,and the like, wherein two or more substituents can be joined together toform a ring; and wherein a Guerbet acetoacetamide refers to anacetoacetamide derived from a Guerbet amine (the Guerbet amine beingderived from a Guerbet alcohol) and an acetonitrile;

wherein in embodiments the number of carbon atoms in R plus R₂ is atleast about 12;

wherein R₂ is (i) an alkyl group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkyl group), in one embodiment with at least about 1 to about 50 carbonatoms, in another embodiment with at least about 2 to about 20 carbonatoms, in another embodiment with at least about 4 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges; (ii) an alkylene group, (including linear, branched, saturated,unsaturated, cyclic, an alkylene group including aliphatic cyclicmoieties therein, unsubstituted, and substituted alkylene groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkylene group), in one embodiment with at least 1 carbon atom, inanother embodiment with at least about 10 carbon atoms, in yet anotherembodiment with at least about 20 carbon atoms, in still anotherembodiment with at least about 36 carbon atoms, in one embodiment withno more than about 200 carbon atoms, in another embodiment with no morethan about 100 carbon atoms, in another embodiment, with no more thanabout 60 carbon atoms, in yet another embodiment with no more than about40 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, in yet another embodiment R₂ is a branched alkylene grouphaving 36 carbon atoms and optionally including unsaturations and cyclicgroups; (iii) an arylene group (including unsubstituted and substitutedarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the arylene group), in one embodiment with at least about6 carbon atoms, in vet another embodiment with at least about 13 carbonatoms; in still another embodiment with at least about 18 carbon atoms,and in yet another embodiment with at least about 23 carbon atoms, andin one embodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 75 carbon atoms, and in yet anotherembodiment with no more than about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges; (iv) an arylalkylenegroup (including unsubstituted and substituted arylalkylene groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present ineither the aryl or the alkyl portion of the arylalkylene group), in oneembodiment with at least about 7 carbon atoms, in another embodimentwith at least about 18 carbon atoms, in yet another embodiment with atleast about 30 carbon atoms, in another embodiment with at least about42 carbon atoms, and in one embodiment with no more than about 200carbon atoms, in another embodiment with no more than about 100 carbonatoms, and in yet another embodiment with no more than about 44 carbonatoms, although the number of carbon atoms can be outside of theseranges; (v) an alkylarylene group, (including unsubstituted andsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the alkyl or the aryl portionof the alkylarylene group), in one embodiment with at least about 7carbon atoms, in yet another embodiment with at least about 18 carbonatoms, in yet another embodiment with at least about 30 carbon atoms, inanother embodiment with at least about 42 carbon atoms, and in oneembodiment with no more than about 200 carbon atoms, in anotherembodiment with no more than about 100 carbon atoms, and in yet anotherembodiment with no more than about 44 carbon atoms, although the numberof carbon atoms can be outside of these ranges; (vi) an alkyleneoxygroup, (including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyleneoxy groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the alkyl portion of thealkyleneoxy group), in one embodiment with at least 1 carbon atom, inanother embodiment with at least about 10 carbon atoms, in anotherembodiment with at least about 20 carbon atoms, and in one embodimentwith no more than about 200 carbon atoms, in another embodiment with nomore than about 100 carbon atoms, in still another embodiment with nomore than about 60 carbon atoms; (vii) an aryleneoxy group, (includingunsubstituted and substituted aryleneoxy groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the aryl portion of thearyleneoxy group), in one embodiment with at least about 6 carbon atoms,in another embodiment with at least about 13 carbon atoms, in stillanother embodiment with at least about 18 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 75 carbon atoms, and in yet anotherembodiment with no more than about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges; (viii) anarylalkyleneoxy group, (including unsubstituted and substitutedarylalkyleneoxy groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the either the aryl or the alkyl portion of thearylalkyleneoxy group), in one embodiment with at least about 7 carbonatoms, in yet another embodiment with at least about 18 carbon atoms, inyet another embodiment with at least about 30 carbon atoms, in anotherembodiment with at least about 42 carbon atoms, and in one embodimentwith no more than about 200 carbon atoms, in another embodiment with nomore than about 100 carbon atoms, and in yet another embodiment with nomore than about 44 carbon atoms, although the number of carbon atoms canbe outside of these ranges; (ix) an alkylaryleneoxy group, (includingunsubstituted and substituted alkylaryleneoxy groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the alkyl or the arylportion of the alkylaryleneoxy group), in one embodiment with at leastabout 7 carbon atoms, in yet another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in another embodiment with at least about 42 carbon atoms, and inone embodiment with no more than about 200 carbon atoms, in anotherembodiment with no more than about 100 carbon atoms, and in yet anotherembodiment with no more than about 44 carbon atoms, although the numberof carbon atoms can be outside of these ranges; (x) a polyalkyleneoxygroup, wherein the alkyl portion of the repeat alkyleneoxy groupstypically has from about 1 to about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as apolyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges; (xi)a polyaryleneoxy group, wherein the aryl portion of the repeataryleneoxy groups typically has from about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges; (xii) a polyarylalkyleneoxy group, wherein the arylalkylportion of the repeat arylalkyleneoxy groups typically has from about 7to about 50 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as a polybenzyleneoxy group, apolyphenylethyleneoxy group, or the like, and wherein the number ofrepeat arylalkyleneoxy groups typically is from about 2 to about 20repeat arylalkyleneoxy groups, although the number of repeat units canbe outside of these ranges; (xiii) a polyalkylaryleneoxy group, whereinthe alkylaryl portion of the repeat alkylaryleneoxy groups typically hasfrom about 7 to about 50 carbon atoms, although the number of carbonatoms can be outside of these ranges, such as a polytolueneoxy group orthe like, and wherein the number of repeat alkylaryleneoxy groupstypically is from about 2 to about 20 repeat alkylaryleneoxy groups,although the number of repeat units can be outside of these ranges;(xiv) a heterocyclic group, (including unsubstituted and substitutedheterocyclic groups), typically with from about 2 to about 12 carbonatoms, and typically with from about 4 to about 18 ring atoms, althoughthe number of carbon atoms and the number of ring atoms can be outsideof these ranges, wherein the heteroatoms in the heterocyclic groups canbe (but are not limited to) nitrogen, oxygen, sulfur, silicon,phosphorus, boron, and the like, as well as mixtures thereof, (xv) asilylene group, (including unsubstituted and substituted silylenegroups); (xvi) a siloxane group, (including unsubstituted andsubstituted siloxane groups); (xvii) a polysilylene group, (includingunsubstituted and substituted polysilylene groups), typically with from2 to about 100 repeat silylene units, or (xviii) a polysiloxane group(including unsubstituted and substituted polysiloxane groups), typicallywith from 2 to about 200 repeat siloxane units, although the number ofrepeat siloxane units can be outside of this range, wherein thesubstituents on the substituted alkylene, arylene, arylalkylene,alkylarylene, alkyleneoxy, aryleneoxy, arylalkyleneoxy, alkylaryleneoxy,polyalkyleneoxy, polyaryleneoxy, polyarylalkyleneoxy,polyalkylaryleneoxy, heterocyclic, silylene, siloxy, polysilylene, andpolysiloxy groups are hydroxy groups, halogen atoms, cyano groups, ethergroups, aldehyde groups, ketone groups, carboxylic acid groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups,cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanatogroups, mixtures thereof, and the like, wherein the substituents on thesilylene, siloxy, polysilylene, and polysiloxy groups can also be alkylgroups, aryl groups, arylalkyl groups, and alkylaryl groups, wherein twoor more substituents can be joined together to form a ring.

Some specific examples of suitable R₂ groups include (but are notlimited to) a menthyl group of the formula

n-hexanediyl, of the formula —(CH₂)₆—, n-octanediyl, of the formula—(CH₂)₈—, n-decanediyl, of the formula —(CH₂)₁₀—, n-dodecanediyl, of theformula —(CH₂)₁₂—, 3-methyl-1,5-pentanediyl, of the formula

1,4-cyclohexanedimethylene, of the formula (which is not intended to belimited to any particular stereochemistry and includes all cis and transisomers)

4,4′-isopropylidenedicyclohexanediyl, of the formula (which is notintended to be limited to any particular stereochemistry and includesall cis and trans isomers)

4,4′-bicyclohexyanediyl, of the formula (which is not intended to belimited to any particular stereochemistry and includes all cis and transisomers)

a branched alkylene group having 36 carbon atoms, including isomers ofthe formula

a branched alkylene group having 36 carbon atoms, including isomers ofthe formula

and other branched alkylene isomers (which may include unsaturations andcyclic groups), 4,8-bis(methylene)tricyclo[5210^(2,6)]decanediyl, of theformula (which is not intended to be limited to any particularstereochemistry and includes all cis and trans isomers)

and the like.

X and X′ if X′ is present, are each independently of the other (i) adirect bond (ii) an oxygen atom (iii) a sulfur atom (iv) a group of theformula —NR₄₀— wherein R₄₀ is a hydrogen atom, an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, unsubstituted, andsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl group), typically with from 1 to about50 carbon atoms, or from about 2 to about 20 carbon atoms, or from about4 to about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryl group (including substituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the aryl group), typically with from about 6 to about 50carbon atoms, or from about 6 to about 20 carbon atoms, or from about 6to about 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an arylalkyl group (including substitutedarylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl portion or the alkyl portion of thearylalkyl group), typically with from about 7 to about 100 carbon atoms,or from about 7 to about 50 carbon atoms, or from about 7 to about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 100 carbon atoms, or fromabout 7 to about 50 carbon atoms, or from about 7 to about 20 carbonatoms, although the number of carbon atoms can be outside of theseranges, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀each, independently of the other, is a hydrogen atom, an alkyl group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl group), typicallywith from 1 to about 50 carbon atoms, or from about 2 to about 20 carbonatoms, or from about 4 to about 12 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, an aryl group (includingsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the aryl group), typically with from about 6 toabout 50 carbon atoms, or from about 6 to about 20 carbon atoms, or fromabout 6 to about 10 carbon atoms, although the number of carbon atomscan be outside of these ranges, an arylalkyl group (includingsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the aryl portion or the alkyl portion of thearylalkyl group), typically with from about 7 to about 100 carbon atoms,or from about 7 to about 50 carbon atoms, or from about 7 to about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 100 carbon atoms, or fromabout 7 to about 50 carbon atoms, or from about 7 to about 20 carbonatoms, although the number of carbon atoms can be outside of theseranges, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, halogen atoms, amine groups, imine groups, ammonium groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, cyanato groups, isocyanato groups,thiocyanato groups, isothiocyanato groups, mixtures thereof, and thelike, wherein two or more substituents can be joined together to form aring and wherein X and X′ can be the same as each other or differentfrom each other.

Z and Z′ are each optionally present, and if present are each,independently of the other (i) a hydrogen atom, (ii) a halogen atom,including fluorine, chlorine, bromine, and iodine, (iii) a nitro group,(iv) an alkyl group (including linear, branched, saturated, unsaturated,cyclic, unsubstituted, and substituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the alkyl group), typicallywith from 1 to about 50 carbon atoms, or about 1 to about 20 carbonatoms; or from about 1 to about 10 carbon atoms although the number ofcarbon atoms can be outside of these ranges, (v) an aryl group(including substituted aryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in the aryl group), typically with fromabout 6 to about 50 carbon atoms, or from about 6 to about 14 carbonatoms, or from about 6 to about 10 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, (vi) an arylalkyl group(including substituted arylalkyl groups, and wherein hetero atoms, suchas oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in the aryl portion or the alkylportion of the arylalkyl group), typically with from about 7 to about 50carbon atoms, or about 7 to about 25 carbon atoms, or from about 7 toabout 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (vii) an alkylaryl group (including substitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 50 carbon atoms, or fromabout 7 to about 25 carbon atoms, or from about 7 to about 15 carbonatoms, although the number of carbon atoms can be outside of theseranges, (viii) a group of the formula

wherein R₇₀ is an alkyl group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkyl group), typically with from 1 to about 50 carbon atoms, or fromabout 1 to about 20 carbon atoms, or from about 1 to about 10 carbonatoms, although the number of carbon atoms can be outside of theseranges, an aryl group (including substituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus,boron, and the like either may or may not be present in the aryl grouptypically with from about 6 to about 50 carbon atoms, or from about 6 toabout 20 carbon atoms, or from about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group (including substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus,boron, and the like either may or may not be present in the aryl portionor the alkyl portion of the arylalkyl group), typically with from about7 to about 50 carbon atoms, or from about 7 to about 25 carbon atoms, orfrom about 7 to about 15 carbon atoms, although the number of carbonatoms can be outside of these ranges, an alkylaryl group (includingsubstituted alkylaryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl portion or the aryl portion of thealkylaryl group), typically with from about 7 to about 50 carbon atoms,or from about 7 to about 25 carbon atoms, or from about 7 to about 15carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an alkoxy group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkoxy groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkyl portion of the alkoxy group), typically with from about 1 to about50 carbon atoms, or from about 4 to about 20 carbon atoms, or from about8 to about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryloxy group (including substituted aryloxygroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the aryl portion of the aryloxy group), typically with fromabout 6 to about 50 carbon atoms, or from about 6 to about 20 carbonatoms, or from about 6 to about 14 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, an arylalkyloxy group(including substituted arylalkyloxy groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the aryl portion or the alkylportion of the arylalkyloxy group), typically with from about 7 to about50 carbon atoms, or from about 7 to about 25 carbon atoms, or from about7 to about 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an alkylaryloxy group (including substitutedalkylaryloxy groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl portion or the aryl portion of the alkylaryloxygroup), typically with from about 7 to about 50 carbon atoms, or fromabout 7 to about 25 carbon atoms, or from about 7 to about 15 carbonatoms, although the number of carbon atoms can be outside of theseranges, a polyalkyleneoxy group, wherein the alkyl portion of the repeatalkyleneoxy groups typically has from about 1 to about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges, apolyaryleneoxy group, wherein the aryl portion of the repeat aryleneoxygroups typically has from about 6 to about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as apolyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, a polyarylalkyleneoxy group, wherein the arylalkyl portionof the repeat arylalkyleneoxy groups typically has from about 7 to about50 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges, a polyalkylaryleneoxy group, wherein the alkylaryl portion ofthe repeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges, a heterocyclic group (includingunsubstituted and substituted heterocyclic groups), typically with fromabout 2 to about 12 carbon atoms, and typically with from about 4 toabout 18 ring atoms, although the number of carbon atoms and the numberof ring atoms can be outside of these ranges, wherein the heteroatoms inthe heterocyclic groups can be (but are not limited to) nitrogen,oxygen, sulfur, silicon, phosphorus, boron, and the like, as well asmixtures thereof, a silyl group (including unsubstituted and substitutedsilyl groups), a siloxane group (including unsubstituted and substitutedsiloxane groups), a polysilylene group (including unsubstituted andsubstituted polysilylene groups), typically with from 2 to about 100repeat silylene units, or a polysiloxane group (including unsubstitutedand substituted polysiloxane groups), typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, (ix) a sulfonyl group of the formula —SO₂R₈₀,wherein R₈₀ is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, unsubstituted, and substitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl group), typically with from 1 to about 50 carbonatoms, or from about 1 to about 20 carbon atoms, and or from about 1 toabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryl group (including substituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the aryl group), typically with from about 6 to about 50carbon atoms, or about 6 to about 20 carbon atoms, or about 6 to about14 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including substituted arylalkyl groupsand wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thearyl portion or the alkyl portion of the arylalkyl group), typicallywith from about 7 to about 50 carbon atoms, or about 7 to about 25carbon atoms, or about 7 to about 15 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an alkylaryl group(including substituted alkylaryl groups, and wherein hereto atoms, suchas oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in the alkyl portion or the arylportion of the alkylaryl group), or about 7 to about 50 carbon atoms, orabout 7 to about 25 carbon atoms, or about 7 to about 15 carbon atoms,although the number of carbon atoms can be outside of these ranges, analkoxy group (including linear, branched, saturated, unsaturated,cyclic, unsubstituted, and substituted alkoxy groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the alkyl portion of thealkoxy group), typically with from about 1 to about 50 carbon atoms, orabout 4 to about 20 carbon atoms, or about 8 to about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, anaryloxy group (including substituted aryloxy groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the aryl portion of thearyloxy group, such as oxygen, nitrogen, sulfur, silicon, phosphorus,boron, and the like either may or may not be present in the aryl portionor the alkyl portion of the arylalkyloxy group), typically with fromabout 6 to about 50 carbon atoms, or about 6 to about 20 carbon atoms,or about 6 to about 14 carbon atoms, although the number of carbon atomscan be outside of these ranges, an arylalkyloxy group (includingsubstituted arylalkyloxy groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in the alkyl portion or the arylportion of the alkylaryloxy group), typically with from about 7 to about50 carbon atoms, or about 7 to about 25 carbon atoms, or about 7 toabout 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an alkylaryloxy group (including substitutedalkylaryloxy groups), typically with from about 7 to about 50 carbonatoms, or about 7 to about 25 carbon atoms, or about 7 to about 15carbon atoms, although the number of carbon atoms can be outside ofthese ranges, a polyalkyleneoxy group, wherein the alkyl portion of therepeat alkyleneoxy groups typically has from about 1 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as a polyethyleneoxy group, a polypropyleneoxy group, apolybutyleneoxy group, or the like, and wherein the number of repeatalkyleneoxy groups typically is from about 2 to about 50 repeatalkyleneoxy groups, although the number of repeat units can be outsideof these ranges, a polyaryleneoxy group, wherein the aryl portion of therepeat aryleneoxy groups typically has from about 6 to about 14 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as a polyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, a polyarylalkyleneoxy group, wherein the arylalkyl portionof the repeat arylalkyleneoxy groups typically has from about 7 to about50 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges, a polyalkylaryleneoxy group, wherein the alkylaryl portion ofthe repeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges, a heterocyclic group (includingunsubstituted and substituted heterocyclic groups), typically with fromabout 2 to about 12 carbon atoms, and typically with from about 4 toabout 18 ring atoms, although the number of carbon atoms and the numberof ring atoms can be outside of these ranges, wherein the heteroatoms inthe heterocyclic groups can be (but are not limited to) nitrogen,oxygen, sulfur, silicon, phosphorus, boron, and the like, as well asmixtures thereof, a silyl group (including unsubstituted and substitutedsilyl groups), a siloxane group (including unsubstituted and substitutedsiloxane groups), a polysilylene group (including unsubstituted andsubstituted polysilylene groups), typically with from 2 to about 100repeat silylene units, or a polysiloxane group (including unsubstitutedand substituted polysiloxane groups), typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, or (x) a phosphoryl group of the formula—PO₃R₉₀, wherein R₉₀ is a hydrogen atom, an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, unsubstituted, andsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl group), typically with from 1 to about50 carbon atoms, or about 1 to about 20 carbon atoms, or about 1 toabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryl group (including substituted arylgroups), typically with from about 6 to about 50 carbon atoms, or about6 to about 20 carbon atoms, or about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group (including substituted arylalkyl groups), typically withfrom about 7 to about 50 carbon atoms, or about 7 to about 25 carbonatoms, or about 7 to about 15 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, an alkylaryl group(including substituted alkylaryl groups), typically with from about 7 toabout 50 carbon atoms, or about 7 to about 25 carbon atoms, or about 7to about 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an alkoxy group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkoxygroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion of the alkoxy group), typically with fromabout 1 to about 50 carbon atoms, or about 4 to about 20 carbon atoms,or about 8 to about 12 carbon atoms, although the number of carbon atomscan be outside of these ranges, an aryloxy group (including substitutedaryloxy groups), typically with from about 6 to about 50 carbon atoms,or about 6 to about 20 carbon atoms, or about 6 to about 14 carbonatoms, although the number of carbon atoms can be outside of theseranges, an arylalkyloxy group (including substituted arylalkyloxygroups), typically with from about 7 to about 50 carbon atoms, or about7 to about 25 carbon atoms, or about 7 to about 15 carbon atoms,although the number of carbon atoms can be outside of these ranges, analkylaryloxy group (including substituted alkylaryloxy groups),typically with from about 7 to about 50 carbon atoms, or about 7 toabout 25 carbon atoms, or about 7 to about 15 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, a polyalkyleneoxygroup, wherein the alkyl portion of the repeat alkyleneoxy groupstypically has from about 1 to about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as apolyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges, apolyaryleneoxy group, wherein the aryl portion of the repeat aryleneoxygroups typically has from about 6 to about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as apolyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, a polyarylalkyleneoxy group, wherein the arylalkyl portionof the repeat arylalkyleneoxy groups typically has from about 7 to about50 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges, a polyalkylaryleneoxy group, wherein the alkylaryl portion ofthe repeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges, a heterocyclic group (includingunsubstituted and substituted heterocyclic groups), typically with fromabout 2 to about 12 carbon atoms, and typically with from about 4 toabout 18 ring atoms, although the number of carbon atoms and the numberof ring atoms can be outside of these ranges, wherein the heteroatoms inthe heterocyclic groups can be (but are not limited to) nitrogen,oxygen, sulfur, silicon, phosphorus, boron, and the like, as well asmixtures thereof, a silyl group (including unsubstituted and substitutedsilyl groups), a siloxane group (including unsubstituted and substitutedsiloxane groups), a polysilylene group (including unsubstituted andsubstituted polysilylene groups), typically with from 2 to about 100repeat silylene units, or a polysiloxane group (including unsubstitutedand substituted polysiloxane groups), typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, wherein the substituents on the substitutedalkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, arylalkoxy,alkylaryloxy, polyalkyleneoxy, polyaryleneoxy, polyarylalkyleneoxy,polyalkylaryleneoxy, heterocyclic, silyl, siloxy, polysilylene, andpolysiloxy groups are hydroxy groups, halogen atoms, cyano groups, ethergroups, aldehyde groups, ketone groups, carboxylic acid groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups sulfide groups, sulfoxide groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups,cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanatogroups, mixtures thereof, and the like, wherein the substituents on thesilylene, siloxy, polysilylene, and polysiloxy groups can also be alkylgroups, aryl groups, arylalkyl groups, and alkylaryl groups, wherein twoor more substituents can be joined together to loran a ring, and whereinZ and Z′ can be the same as each other or different from each other. Upto 4 Z groups can be present on the molecule. Up to 4 Z′ groups can bepresent on the molecule. The groups Z and X can be joined together toform a ring and the groups Z′ and X′ can be joined together to form aring.

For example, in embodiments wherein X or X and X′ is oxygen, compoundsdisclosed herein include but are not limited to compounds of the formula

Some specific examples include, but are not limited to,

wherein R, R′ is an N-substituted acetoacetamide;

and the like. Colorants of the present disclosure can be prepared by anydesired or effective procedure. For example, they can be prepared bydiazotization of the correspondingly substituted dimeric anthranilatecompound with nitrosylsulfuric acid under cold temperature conditions,followed by coupling with the correspondingly substituted acetoacetamidoin a buttered alkaline aqueous solution under cold temperatureconditions, as follows:

Other methods can be employed including use of KNO₂ or NaNO₂ and amineral acid such as HCl or H₂SO₄. More specifically, thecorrespondingly substituted dianthranilate is first subjected to adiazotization reaction by dissolving it in acetic acid diluted with asolvent and, optionally, a second acid, such as sulfuric acid,dodecylbenzene sulfonic acid, propionic acid, hydrochloric acid,phosphoric acid, any other acid useful for a diazotization reaction, orthe like, as well as mixtures thereof. The solvent can be any solventuseful in a diazotization reaction, such as water, acetone,dimethylformamide, dimethyacetamide, tetrahydrofuran, dimethoxyethane,analogous higher-boiling ether solvents, and the like, as well asmixtures thereof.

The solvent and the dianthranilate are present in any desired oreffective relative amounts; if, for purposes of determining relativeamounts, “solvent” is defined to include whatever solvent has beenselected plus any amount of acetic acid and second acid present, thereactants are present in this combined solvent in relative amounts of inone embodiment at least about 100 grams of substituted dianthranilateper liter of solvent, in another embodiment at least about 200 grams ofsubstituted dianthranilate per liter of solvent, and in yet anotherembodiment at least about 230 grams of substituted dianthranilate perliter of solvent, and in one embodiment of no more than about 400 gramsof substituted dianthranilate per liter of solvent, in anotherembodiment of no more than about 300 grams of substituted dianthranilateper liter of solvent, and in yet another embodiment of no more thanabout 270 grams of substituted dianthranilate per liter of solvent,although the relative amounts can be outside of these ranges.

The acetic acid is present in any desired or effective amount, in oneembodiment at least about 1 gram of acetic acid per gram of substituteddianthranilate, in another embodiment at least about 2 grams of aceticacid per gram of substituted dianthranilate, and in yet anotherembodiment at least about 3 grams of acetic acid per gram of substituteddianthranilate, and in one embodiment no more than about 10 grams ofacetic acid per gram of substituted dianthranilate, in anotherembodiment no more than about 7 grams of acetic acid per gram ofsubstituted dianthranilate, and in yet another embodiment no more thanabout 5 grams of acetic acid per gram of substituted dianthranilate,although the relative amounts can be outside of these ranges.

When present, the optional second acid is present in any desired oreffective amount, in one embodiment at least about 0.05 gram of acid pergram of substituted dianthranilate, and in another embodiment at leastabout 0.1 gram of acid per gram of substituted dianthranilate, and inone embodiment no more than about 0.5 grams of acid per gram ofsubstituted dianthranilate, in another embodiment no more than about 0.3grams of acid per gram of substituted dianthranilate, and in yet anotherembodiment no more than about 0.2 grams of acid per gram of substituteddianthranilate, although the relative amounts can be outside of theseranges.

In the mixture comprising the selected solvent, any optional secondacid, and acetic acid, the acetic acid is present in any desired oreffective amount, in one embodiment at least about 50 percent by volumeof the mixture, in another embodiment at least about 70 percent byvolume of the mixture, in yet another embodiment at least about 75percent by volume of the mixture, and in still another embodiment atleast about 95 percent by volume of the mixture, although the relativeamount can be outside of these ranges.

Upon complete dissolution of the ingredients, the mixture is cooled, inone embodiment to a temperature of no more than about +15° C., inanother embodiment to a temperature of no more than about +10° C., inyet another embodiment to a temperature of no more than about +5° C., instill another embodiment to a temperature of no more than about +3° C.,and in one embodiment to a temperature of no lower than about −5° C.,and in another embodiment to a temperature of no lower than about −10°C., although the temperature can be outside of these ranges.

Thereafter, nitrosylsulfuric acid, or other acid if other method isemployed, is added to the mixture in any desired or effective amount, inone embodiment at least about 2 moles of nitrosylsulfuric acid per moleof substituted dianthranilate (i.e., at least about 1 mole ofnitrosylsulfuric acid per mole of aniline moiety in the dianthranilate),and in another embodiment at least about 2.1 moles of nitrosylsulfuricacid per mole of substituted dianthranilate, and in one embodiment nomore than about 3 moles of nitrosylsulfuric acid per mole of substituteddianthranilate, in another embodiment no more than about 2.5 moles ofnitrosylsulfuric acid per mole of substituted dianthranilate, and in yetanother embodiment no more than about 2.25 moles of nitrosylsulfuricacid per mole of substituted dianthranilate, although the relativeamounts can be outside of these ranges. In a specific embodiment, thenitrosylsulfuric acid is added dropwise at a rate such that thetemperature of the reaction mixture does not exceed 15° C.

The reaction to form the diazonium salt is essentially instantaneous,and upon completion of addition of the nitrosylsulfuric acid thereaction is essentially complete. At times, the reaction can take aperiod of time to complete, from instantaneous to about 6 hours. Ifdesired, a qualitative test can be performed to confirm reactioncompletion.

Thereafter, residual excess nitrosylsulfuric acid present in thereaction mixture can be quenched by the addition of a quenching agent,such as sulfamic acid, urea, or the like as well as mixtures thereof, inany desired or effective amount, in one embodiment at least about 0.01mole of quenching agent per mole of nitrosylsulfuric acid (i.e., permole of nitrosylsulfuric acid originally added to the reaction mixture),in another embodiment at least about 0.05 mole of quenching agent permole of nitrosylsulfuric acid, and in yet another embodiment at leastabout 0.1 mole of quenching agent per mole of nitrosylsulfuric acid, andin one embodiment no more than about 0.5 mole of quenching agent permole of nitrosylsulfuric acid, in another embodiment no more than about0.3 mole of quenching agent per mole of nitrosylsulfuric acid, and inyet another embodiment no more than about 0.2 mole of quenching agentper mole of nitrosylsulfuric acid, although the amount can be outside ofthese ranges. Upon completion of the reaction, the reaction mixturecontains the corresponding diazonium salt.

A precursor solution of the acetoacetamide having the desiredsubstituents thereon is prepared neat, or in an appropriate solvent,such as a mixture of water, organic solvents, including lower alcoholssuch as methanol, ethanol, isopropanol, and the like, water-misciblenonbasic organic solvents such as tetrahydrofuran, acetone,dimethoxyethane, N,N-dimethylformamide, N,N-dimethylacetamide,acetonitrile, and the like, as well as mixtures thereof. Mixtures ofwater with an organic solvent can be helpful for ease of solvatinginorganic or organic salts that are a reaction by-product. In thisinstance, water and the organic solvent are present in any desired oreffective relative amounts, in one embodiment at least about 0.25 gramof organic solvent per gram of water, in another embodiment at leastabout 0.3 gram of organic solvent per gram of water, and in yet anotherembodiment at least about 0.4 gram of organic solvent per gram of water,and in one embodiment no more than about 4 grams of organic solvent pergram of water, in another embodiment no more than about 3 grams oforganic solvent per gram of water, and in yet another embodiment no morethan about 2 grams of organic solvent per gram of water, although therelative amounts can be outside of these ranges.

The acetoacetamide is present in the precursor solution in any desiredor effective amount, in one embodiment at least about 10 grams ofacetoacetamide per liter of solvent, in another embodiment at leastabout 30 grams of acetoacetamide per liter of solvent, and in yetanother embodiment at least about 50 grams of acetoacetamide per literof solvent per liter of solvent per liter of no more than about 200grams of acetoacetamide per liter of solvent, in another embodiment nomore than about 100 grams of acetoacetamide per liter of solvent, and inyet another embodiment no more than about 70 grams of acetoacetamide perliter of solvent, although the relative amounts can be outside of theseranges.

The acetoacetamide precursor solution is prepared, the acetonitrile isdistilled off, and the product is stored in a jar. It doesn't say thatthe product is stored in an alkaline solution. If desired, theacetoacetamide precursor solution can be maintained at an alkaline pH,typically of at least about 10, and in one embodiment no more than about14, and in another embodiment no more than about 12, although the pH canbe outside of these ranges. The acetoacetamide precursor solution cancontain a mixture of a base and an optional buffering salt.

Examples of suitable bases include mineral bases, such as sodiumhydroxide, potassium hydroxide, and the like, as well as water-miscibleorganic tertiary amines, such as triethanolamine,N,N-diethylethanolamine, and the like, as well as mixtures thereof,present in any desired or effective amount, in one embodiment at leastabout 1 mole of base per mole of acetoacetamide, in another embodimentat least about 2 moles of base per mole of acetoacetamide, in yetanother embodiment at least about 3 moles of base per mole ofacetoacetamide, and in still another embodiment at least about 5 motesof base per mole of acetoacetamide, and in one embodiment no more thanabout 10 moles of base per mole of acetoacetamide, in another embodimentno more than about 7 moles of base per mole of acetoacetamide, and inyet another embodiment no more than about 5 moles of base per mole ofacetoacetamide, although the relative amounts can be outside of theseranges.

Examples of suitable optional buffer salts include those correspondingto the principal acid solvent; for example, when the principal acidsolvent is acetic acid, suitable buffers include sodium acetate,potassium acetate, sodium hydrogenphosphate, citric acid, and the like,as well as mixtures thereof. When present, the optional buffer salt ispresent in any desired or effective amount, in one embodiment at leastabout 1 mole of buffer per mole of acetoacetamide, in another embodimentat least about 2 moles of buffer per mole of acetoacetamide, in yetanother embodiment at least about 3 moles of buffer per mole ofacetoacetamide, and in still another embodiment at least about 5 molesof buffer per mole of acetoacetamide, and in one embodiment no more thanabout 10 moles of buffer per mole of acetoacetamide, in anotherembodiment no more than about 7 moles of buffer per mole ofacetoacetamide, and in yet another embodiment no more than about 5 molesof buffer per mole of acetoacetamide, although the relative amounts canbe outside of these ranges. In a specific embodiment, upon dissolutionof the acetoacetamide, the thus-formed precursor acetoacetamide solutioncan be filtered to remove any undissolved solids.

The solution containing the diazonium sail, maintained at a coldtemperature, is then slowly added to the acetoacetamide solution in anydesired or effective relative amounts. If the diazonium salt is of adimeric species (that is, a bis-diazonium salt), in one embodiment atleast about 2 moles of acetoacetamide per mole of diazonium salt, inanother embodiment at least about 2.1 moles of acetoacetamide per moleof diazonium salt, and in yet another embodiment at least about 2.25moles of acetoacetamide per mole of diazonium salt, and in oneembodiment no more than about 4 moles of acetoacetamide per mole ofdiazonium salt, in another embodiment no more than about 3 moles ofacetoacetamide per mole of diazonium salt, and in vet another embodimentno more than about 2.5 moles of acetoacetamide per mole of diazoniumsalt, if a monomeric diazonium salt is selected, the moles ofacetoacetamide should be halved, although the relative amounts can beoutside of these ranges, resulting in the immediate formation of abright yellow precipitate. Thereafter, the yellow precipitate can becollected by filtration and, if desired, washed.

In embodiments, a reaction scheme herein includes, for example,

Precursor dianthranilates can be prepared by any desired or effectivemethod, such as that disclosed in, for example, U.S. Pat. No. 6,713,614and U.S. Pat. No. 6,576,747; the disclosures of each of which aretotally incorporated herein by reference. Precursor acetoacetamides canbe prepared by any desired or effective method, such as that disclosedin, for example, Chemical Reviews, 1986, Vol. 86, No. 2, pp. 241-258, byRobert Clemens, which is incorporated herein by reference.

While not being limited to any particular theory, it is believed that inembodiments the structure of the present compounds provide improvedmigratory and diffusion properties. Further, while not being limited toany particular theory, it is believed that in embodiments the waxyappendages (that is, long chains) protruding from the chromophore ateach end provide a compound that is compatible and soluble in the phasechange ink base. It is believed that this structural feature can alsoimpart thermal stability and chemical stability to the colorantmolecule. Further, while not being limited to any particular theory, itis believed that including alkyl or alkylene groups with at least about12 carbon atoms, particularly (although not necessarily) branched alkylgroups of this type, in the colorant molecule further reduce diffusionor leaching of the colorant molecule from a medium such as a phasechange ink vehicle into adjacent inks of different colors (leading tointercolor bleed), adjacent unprinted areas (leading to edgeraggedness), tape adhesives (leading to edge raggedness and possibleillegibility), and the like.

In addition to being suitable for use in phase change inks, thecolorants of the present disclosure can be used in applications such astextile dyeing, biological dyeing applications that rely on highspectral strength chromophores, electronics applications, such asorganic photoconductors, optical filters, and the like, color filtersfor liquid crystal display systems, and the like.

Phase change inks of the present disclosure contain a phase changecarrier system or composition. The phase change carrier composition istypically designed for use in either a direct printing mode or anindirect or offset printing transfer system. In the direct printingmode, the phase change carrier composition in one embodiment containsone or more materials that enable the phase change ink (1) to be appliedin a thin film of uniform thickness on the final recording substrate(such as paper, transparency material, and the like) when cooled toambient temperature after printing directly to the recording substrate,(2) to be ductile while retaining sufficient flexibility so that theapplied image on the substrate will not fracture upon bending, and (3)to possess a high degree of lightness, chroma, transparency, and thermalstability. In an offset printing transfer or indirect printing mode, thephase change carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference

Any desired or effective carrier composition can be used. Examples ofsuitable ink carrier materials include fatty amides, such as monoamides,tetraamides, mixtures thereof, and the like. Specific examples ofsuitable fatty amide ink carrier materials include stearyl stearamide, adimer acid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and stearic acid, a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, and the like, aswell as mixtures thereof. When the fatty amide ink carrier is a dimeracid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and a carboxylic acid having at least about 36 carbonatoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, andBritish Patent GB 2 238 792, the disclosures of each of which aretotally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 6,525,161, U.S. Pat. No. 5,750,604, U.S. Pat. No.5,780,528, U.S. Pat. No. 5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat.No. 5,827,918, U.S. Pat. No. 5,830,942, U.S. Pat. No. 5,919,839, U.S.Pat. No. 6,255,432, U.S. Pat. No. 6,309,453, British Patent GB 2 294939, British Patent GB 2 305 928, PCT Publication WO 94/14902, and PCTPublication WO 95/04760, the disclosures of each of which are totallyincorporated herein by reference. Mixtures of fatty amide materials andisocyanate-derived materials can also be employed as the ink carriercomposition for inks of the present disclosure.

Additional suitable phase change ink carrier materials for the presentdisclosure include paraffins, microcrystalline waxes, polyethylenewaxes, ester waxes, amide waxes, fatty acids, fatty alcohols, fattyamides and other waxy materials, sulfonamide materials, resinousmaterials made from different natural sources (such as, for example,tall oil rosins and rosin esters), and many synthetic resins, oligomers,polymers and copolymers, such as ethylene/vinyl acetate copolymers,ethylene/acrylic acid copolymers, ethylene/vinyl acetate/acrylic acidcopolymers, copolymers of acrylic acid with polyamides, and the like,ionomers, and the like, as well as mixtures thereof. One or more ofthese materials can also be employed in a mixture with a fatty amidematerial and/or an isocyanate-derived material.

In one specific embodiment, the phase change ink carrier comprises theink carrier comprises (a) a polyethylene wax, present in the ink in anamount in one embodiment of at least about 25 percent by weight of theink, in another embodiment of at least about 30 percent by weight of theink, and in yet another embodiment of at least about 37 percent byweight of the ink, and in one embodiment of no more than about 60percent by weight of the ink, in another embodiment of no more thanabout 53 percent by weight of the ink, and ink, although the amount canbe outside of these ranges; (b) a stearyl stearamide wax, present in theink in an amount in one embodiment of at least about 8 percent by weightof the ink, in another embodiment of at least about 10 percent by weightof the ink, and in yet another embodiment of at least about 12 percentby weight of the ink, and in one embodiment of no more than about 32percent by weight of the ink, in another embodiment of no more thanabout 28 percent by weight of the ink, and in yet another embodiment orno more than about 25 percent by weight of the ink, although the amountcan be outside of these ranges; (c) a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid derivative of a long chain alcohol having greater thanthirty six carbon atoms, present in the ink in an amount in oneembodiment of at least about 10 percent by weight of the ink, in anotherembodiment of at least about 13 percent by weight of the ink, and in yetanother embodiment of at least about 16 percent by weight of the ink,and in one embodiment of no more than about 32 percent by weight of theink, in another embodiment of no more than about 27 percent by weight ofthe ink, and in yet another embodiment of no more than about 22 percentby weight of the ink, although the amount can be outside of theseranges; (d) a urethane resin derived from the reaction of twoequivalents of hydroabietyl alcohol and one equivalent of isophoronediisocyanate, present in the ink in an amount in one embodiment of atleast about 6 percent by weight of the ink, in another embodiment of atleast about 8 percent by weight of the ink, and in yet anotherembodiment of at least about 10 percent by weight of the ink, and in oneembodiment of more than about 16 percent by weight of the ink, inanother embodiment of no more than about 14 percent by weight of theink, and in yet another embodiment of no more than about 12 percent byweight of the ink, although the amount can be outside of these ranges;(e) a urethane resin that is the adduct of three equivalents of stearylisocyanate and a glycerol-based alcohol, present in the ink in an amountin one embodiment of at least about 2 percent by weight of the ink, inanother embodiment of at least 3 percent by weight of the ink, and inyet another embodiment of at least about 4.5 percent by weight of theink, and in one embodiment of no more than about 13 percent by weight ofthe ink, in another embodiment of no more than about 10 percent byweight of the ink, and in yet another embodiment of no more than about7.5 percent by weight of the ink, although the amount can be outside ofthese ranges; and (f) an antioxidant, present in the ink in an amount inone embodiment of at least about 0.01 percent by weight of the ink, inanother embodiment of at least about 0.05 percent by weight of the ink,and in yet another embodiment of at least about 0.1 percent by weight ofthe ink, and in one embodiment of no more than about 1 percent by weightof the ink, in another embodiment of no more than about 0.5 percent byweight of the ink, and in yet another embodiment of no more than about0.3 percent by weight of the ink, although the amount can be outside ofthese ranges.

The ink carrier is present in the phase change ink of the presentdisclosure in any desired or effective amount, in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 50 percent by weight of the ink, and in yet anotherembodiment of at least about 90 percent by a weight of the ink, and inone embodiment of no more than about 99 percent by weight of the ink, inanother embodiment of no more than about 98 percent by weight of theink, and in yet another embodiment of no more than about 95 percent byweight off the ink, although the amount can be outside of these ranges.

The phase change inks of the present disclosure contains a colorantcompound of the formula as disclosed herein. This colorant is present inthe ink in any desired or effective amount to obtain the desired coloror hue, in one embodiment of at least about 1 percent by weight of theink, in another embodiment of at least about 2 percent by weight of theink, and in yet another embodiment of at least about 3 percent by weightof the ink, and in one embodiment of no more than about 20 percent byweight of the ink, in another embodiment of no more than about 13percent by weight of the ink, and in yet another embodiment of no morethan about 6 percent by weight of the ink, although the amount can beoutside of these ranges. The colorant according to the presentdisclosure can either be the sole colorant in the ink or can be presentin combination with other colorants, such as dyes, pigments, mixturesthereof, and the like.

The inks of the present disclosure can also optionally contain anantioxidant. The optional antioxidants of the ink compositions protectthe images from oxidation and also protect the ink components fromoxidation during the heating portion of the ink preparation process.Specific examples of suitable antioxidants include NAUGUARD® 524,NAUGUARD® 76, and NAUGUARD® 512, commercially available from UniroyalChemical Company, Oxford, Conn., IRGANOX® 1010, commercially availablefrom Ciba Geigy, and the like. When present, the optional antioxidant ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.01 percent by weight of the ink, in anotherembodiment of at least about 0.1 percent by weight of the ink, and inyet another embodiment of at least about 1 percent by weight of the ink,and in one embodiment of no more than about 20 percent by weight of theink, in another embodiment of no more than about 5 percent by weight ofthe ink, and in yet another embodiment of no more than about 3 percentby weight of the ink, although the amount can be outside of theseranges.

The inks of the present disclosure can also optionally contain aviscosity modifier. Examples of suitable viscosity modifiers includealiphatic ketones, such as stearone, and the like. When present, theoptional viscosity modifier is present in the ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan actual 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 15 percent by weight of the ink,although the amount can be outside of these ranges. Other optionaladditives to the inks include clarifiers, such as UNION CAMP®X37-523-235 (commercially available from Union Camp), in an amount inone embodiment of at least about 0.01 percent by weight of the ink, inanother embodiment of at least about 0.1 percent by weight of the ink,and in yet another embodiment of at least about 5 percent by weight ofthe ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, tackifiers, such as FORAL® 85, a glycerol esterof hydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 Resin, a triglyceride ofhydrogenated abietic (rosin) acid (commercially available from ArakawaChemical Industries, Ltd.), synthetic polyterpene resins such as NEVTAC®2300, NEVTAC® 100, and NEVTAC® 80 (commercially available from NevilleChemical Company), WINGTACK® 86, a modified synthetic polyterpene resin(commercially available from Goodyear), and the like, in an amount inone embodiment of at least about 0.1 percent by weight of the ink, inanother embodiment of at least about 5 percent by weight of the ink, andin yet another embodiment of at least about 10 percent by weight of theink, and in one embodiment of no more than about 98 percent by weight ofthe ink, in another embodiment of no more than about 75 percent byweight of the ink, and in yet another embodiment of no more than about50 percent by weight of the ink, although the amount can be outside ofthese range, adhesives, such as VERSAMID® 757, 759, or 744 (commerciallyavailable from Henkel), in an amount in one embodiment of at least about0.1 percent by weight of the ink, in another embodiment of at mast about1 percent by weight of the ink, and in yet another embodiment of atleast about 5 percent by weight of the ink, and in one embodiment of nomore than about 98 percent by weight of the ink, in another embodimentof no more than about 50 percent by weight of the ink, and in yetanother embodiment of no more than about 10 percent by weight of theink, although the amount can be outside of these ranges, plasticizers,such as UNIPLEX® 250 (commercially available from Uniplex), thephthalate ester plasticizers commercially available from Monsanto underthe trade name SANTICIZER®, such as dioctyl phthalate, diundecylphthalate, alkylbenzyl phthalate (SANTICIZER® 278), triphenyl phosphate(commercially available from Monsanto), KP-140®, a tributoxyethylphosphate (commercially available from FMC Corporation), MORFLEX® 150, adicyclohexyl phthalate (commercially available from Morflex ChemicalCompany Inc.), trioctyl trimellitate (commercially available fromEastman Kodak Co.), and the like, in an amount in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 1 percent by weight of the ink, and in yet anotherembodiment of at least about 2 percent by weight of the ink, and in oneembodiment of no more than about 50 percent by weight of the ink, inanother embodiment of no more than about 30 percent by weight of theink, and in yet another embodiment of no more than about 10 percent byweight of the ink, although the amount can be outside of these ranges,and the like.

The ink compositions of the present disclosure in one embodiment havemelting points of no lower than about 50° C., in another embodiment ofno lower than about 70° C., and in yet another embodiment of no lowerthan about 80° C., and have melting points in one embodiment of nohigher than about 160° C., in another embodiment of no higher than about140° C., and in yet another embodiment of no higher than about 100° C.,although the melting point can be outside of these ranges. The inkcompositions of the present disclosure generally have melt viscositiesat the jetting temperature (in one embodiment no lower than about 75°C., in another embodiment lower than about 100° C., and in yet anotherembodiment no lower than about 120° C., an in another embodiment, about140° C., and in one embodiment no higher than about 180° C., and inanother embodiment no higher than about 150° C., although the jettingtemperature can be outside of these ranges) in one embodiment of no morethan about 30 centipoise, in another embodiment of no more than about 20centipoise, and in yet another embodiment of no more than about 15centipoise, and in one embodiment of no less than about 1 centipoise,and in another embodiment of no less than about 2 centipoise, in anotherembodiment of no less than about 5 centipoise, and in yet anotherembodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

The ink compositions of the present disclosure can be prepared by anydesired or suitable method. For example, the ink ingredients can bemixed together, followed by heating, to a temperature in one embodimentof at least about 100° C., and in one embodiment of no more than about140° C., although the temperature can be outside of these ranges, andstirring until a homogeneous ink composition is obtained, followed bycooling the ink to ambient temperature (typically from about 20 to about25° C.). The inks of the present disclosure are solid at ambienttemperature. In a specific embodiment, during the formation process, theinks in their molten state are poured into molds and then allowed tocool and solidify to form ink sticks.

The inks of the present disclosure can be employed in apparatus fordirect printing ink jet processes and in indirect (offset) printing inkjet applications. Another embodiment of the present disclosure isdirected to a process which comprises incorporating an ink of thepresent disclosure into an ink jet printing apparatus, melting the ink,and causing droplets of the melted ink to be ejected in an imagewisepattern onto a recording substrate. A direct printing process is alsodisclosed in, for example, U.S. Pat. No. 5,195,430, the disclosure ofwhich is totally incorporated herein by reference. In embodiments, thesubstrate is a final recording sheet and droplets of the melted ink areejected in an imagewise pattern directly onto the final recording sheet.Yet another embodiment of the present disclosure is directed to aprocess which comprises incorporating an ink of the present disclosureinto an ink jet printing apparatus, melting the ink, causing droplets ofthe melted ink to be ejected in an imagewise pattern onto anintermediate transfer member, and transferring the ink in the imagewisepattern from the intermediate transfer member to a final recordingsubstrate in embodiments, the intermediate transfer member is heated toa temperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. An offset or indirect printingprocess is also disclosed in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference. In onespecific embodiment, the printing apparatus employs a piezoelectricprinting process wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.Inks of the present disclosure can also be employed in other hot meltprinting processes, such as hot melt acoustic ink jet printing, hot meltthermal ink jet printing, hot melt continuous stream or deflection inkjet printing, and the like. Phase change inks of the present disclosurecan also be used in printing processes other than hot melt ink jetprinting processes. Any suitable substrate or recording sheet can beemployed, including plain papers such as XEROX® 4024 papers, XEROX®Image Series papers, Courtland 4024 DP paper, ruled notebook paper, bondpaper, silica coated papers such as Sharp Company silica coated paper,JuJo paper, Hammermill Laserprint Paper, and the like, transparencymaterials, fabrics, textile products, plastics, polymeric films,inorganic substrates such as metals and wood, and the like.

The following Examples are being submitted to further define variousspecies of the present disclosure. These Examples are intended to beillustrative only and are not intended to limit the scope of the presentdisclosure. Also, parts and percentages are by weight unless otherwiseindicated.

EXAMPLE 1

Synthesis of 2-ethylhexylacetoacetamide. An acetoacetamide compound ofthe formula

was prepared as follows. Into a 250 milliliter 3-neck round bottom flaskequipped with a magnetic stirrer, a silicone oil bath and a condenserwas charged 38.4 grams of 2-ethylhexylamine (MW=129) and about 100 gramsof acetonitrile. With stirring at room temperature, about 25.0 grams ofdiketene (MW=84) was added. An exotherm was observed. The round bottomflask was put in an 80° C. oil bath and refluxed for about 3 hours. Theacetonitrile was distilled off and the temperature of the reactionincreased to 120° C. for about 2 hrs. The product was poured into a jar.

EXAMPLE 2

Synthesis of Dodecylanilineacetoacetamide. An acetoacetamide compound ofthe formula

was prepared as follows. To a 500 milliliter 3-neck round bottom flaskequipped with magnetic stirrer, a silicone oil bath and a condenser wascharged about 77.7 grams of dodecylaniline (MW=261, available fromEMF-Dottikon), about 25.0 grams of diketene (MW=84) and about 150 gramsof acetonitrile. With stirring at room temperature, about 25.0 grams ofdiketene (MW=84) was added. An exotherm was observed. The round bottomflask was put in an 80° C. oil bath and refluxed for about 3 hours. Theacetonitrile was distilled off and the temperature of the reactionincreased to about 120° C. for about 2 hours. The product was pouredinto a jar.

EXAMPLE 3

Synthesis of Guerbet-acetoacetamide. An acetoacetamide compound of theformula

was prepared as follows. To a 250 milliliter 3-neck round bottom flaskequipped with magnetic stirrer, a silicone oil bath and a condenser wascharged about 42.3 grams of PA-24 (MW=355 Guerbet amine available fromthe Tomah Chemical Co.) and about 75 grams of acetonitrile. The twochemicals were not miscible. When about 10.0 grams of diketene (MW=84)was added, an exotherm was observed and all chemicals became miscible.The round bottom flask was placed in an about 80° C. oil bath andrefluxed for about 1 hour. The acetonitrile was distilled off and thetemperature of the reaction increased to about 120° C. for about 1hours. The product was poured into a jar.

EXAMPLE 4

Synthesis of p-hydroxyethylanilino-acetoacetamide. An acetoacetamidecompound of the formula

was prepared as follows. To a 100 milliliter 3-neck round bottom flaskequipped with magnetic stirrer, a silicone oil bath and a condenser wascharged about 16.3 grams 4-aminophenethyl alcohol (available from AcetoCorporation, MW=137) and about 75 grams of acetonitrile. It did nottotally dissolve. About 10.0 grams of diketene (MW=84) was added. Theround bottom flask was placed in an about 80° C. oil bath and refluxedfor about 1 hour. All dissolved. The acetonitrile was distilled off andthe temperature of the reaction increased to about 120° C. for about 2hours. The product was poured into ajar

EXAMPLE 5—PART A

Synthesis of Dimer Dianthranilate Bis-(2-ethylhexylacetoacetamide) Azo.Part A: Dimer Dianthranilate Bis-Diazotization. To a 1 liter 3-neckround bottom flask equipped with mechanical stirrer, a silicone oil bathand a thermometer was charged about 21.6 grams (MW=776) of dimer esteranthranilate (DEA) precursor (the preparation of which is found inExample 1 of U.S. Pat. No. 6,713,614, the disclosure of which is herebyincorporated by reference herein in its entirety) followed sequentiallywith about 42 milliliters of glacial acetic acid about 3-6 millilitersof concentrated sulfuric acid, about 4.0 milliliters of deionized waterand about 4.4 milliliters of propionic acid. All dissolved. The roundbottom flask was put in an ice bath and stirred until the temperaturewas about 3° C. to about 5° C. To a constant pressure addition funnelwas charged about 11.2 milliliters (0.057 moles) of nitrosyl sulfuricacid (NSA, MW=127, 40% by weight in sulfuric acid). The NSA solution wasadded slowly into the brown DEA solution to maintain the reactiontemperature between about 3° C. to about 10° C. After about 2 hours, theaddition was complete and the contents were stirred for another halfhour. A phosphomolybdic acid test (PMA test) was run to determine if thereaction was completed. The result was negative which suggested thereaction had not completed and more NSA was needed. About 1.0 gadditional NSA was added. After about 15 minutes, a PMA test was run andthe result was still negative. About 0.4 g NSA was added. After about 15minutes, another PMA test was run and the result was negative. Anotherabout 0.4 grams of NSA was added and another PMA test was run. This timethe result was positive. Then about 0.6 gram of sulfamic acid was addedto react with excess NSA. A PMA test was run after about 15 minutes andit indicated that all NSA was reacted. At this point the azo was readyto add to the coupler.

EXAMPLE 5 Part B

Synthesis of Dimer Dianthranilate Bis-(2-ethylhexylacetoacetamide) Azo.Part B: The Coupling of Dimer Dianthranilate Bis-Diazo to2-Ethylhexylacetoacetamide. A compound of the formula

was prepared as follows. Dissolving the 2-ethylhexylacetoacetamide: To a2 liter beaker equipped with a magnetic stir bar was charged about 700grams of deionized water, about 16.0 grams of acetic acid, and about22.2 grams of sodium hydroxide. The contents were stirred untilcompletely dissolved. About 700 milliliters of isopropyl alcohol andabout 11.8 grams of 2-ethylhexylacetoacetamide from Example 1 above wasthen added and stirred until all was dissolved.

Adding the Dimer Dianthranilate Bis-Diazo to the Dissolved2-ethylhexylacetoacetamide: The cooled contents from Example 5, Part Awere slowly added to the beaker containing the2-ethylhexylacetoacetamide solution. A yellow precipitate formed at thebeginning of coupling and then the solids turned into a very viscousliquid. After stirring for about one hour, the contents were allowed tosettle over night. The top liquid was decanted. The bottom viscousliquid contained white salt and yellow product. About 700 milliliters ofdeionized water was added to the solids and stirred for about one hour.The aqueous layer was then discarded. The bottom yellow viscous liquidproduct was dissolved in about 300 milliliters of toluene and washedwith water in a separatory funnel. The lower water layer was discardedand the top toluene layer was run through a silica plug. Then thetoluene was evaporated yielding a viscous very dark yellow dye. Thespectral strength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured in toluene was about 35,330mL*Absorbance Units per gram at absorption λ_(max).

EXAMPLE 6

The Coupling of Dimer Dianthranilate Bis-Diazo tododecylanilineacetoacetamide. A compound of the formula

was prepared as follows. Dissolving the dodecylanilinoacetoacetamide: Toa 4 liter beaker with magnetic stir bar was charged about 700 grams ofdeionized water, about 16.0 grams of acetic acid, and about 22.2 gramsof sodium hydroxide. The contents were stirred until completelydissolved. About 1700 milliliters isopropyl alcohol and about 18.8 gramsof dodecylanthneacetoacetamide from Example 2 above was then added andstirred until dissolved.

Adding the Dimer Dianthranilate Bis-Diazo to the DissolvedDodecylanilino-acetoacetamide: The cooled contents from Example 5, PartA above were slowly added to the beaker containing thedodecylanilinoacetoacetamide solution. A yellow precipitate formed atthe beginning of coupling, and then the solids turned into a veryviscous liquid. At the end of coupling two types of solids formed. Onewas yellow sticky solid while the other was a very fine solid. Afterstirring for about one hour the contents were allowed to settle overnight. The top liquid was decanted. The sticky solid was easilyseparated from the very fine solid which turned out to be salts and wereremoved by dissolving in water. The sticky yellow solid was dissolved inabout 300 milliliters of toluene and washed with water in a separatoryfunnel. The lower water layer was discarded and the top toluene layerwas run through a silica plug. Then the solvent was evaporated yieldinga viscous very dark yellow dye. The spectral strength of the yellowcolorant was determined using a spectrophotometric procedure based onthe measurement of the colorant in solution by dissolving the colorantin toluene and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the colorant measuredin toluene as about 30,285 mL*Absorbance Units per gram at absorptionλ_(max).

EXAMPLE 7

The Coupling of Dimer Dianthranilate Bis-Diazo toGuerbet-acetoacetamide. A compound of the formula

was prepared as follows. Dissolving the Guerbet-acetoacetamide: To a 4liter beaker with magnetic stir bar was charged about 700 grams ofdeionized water, about 16.0 grams of acetic acid, and about 22.2 gramsof sodium hydroxide. The contents were stirred until completelydissolved About 2300 milliliters isopropyl alcohol and about 24.0 gramsof Guerbet-acetoacetamide from Example 3 above was then added andstirred until dissolved.

Adding the Dimer Dianthranilate Bis-Diazo to the DissolvedGuerbet-acetoacetamide: The cooled contents from Example 5, Part A abovewere slowly added to the beaker containing the Guerbet-acetoacetamidesolution. A yellow precipitate formed at the beginning of coupling thenthe dissolved in about 300 milliliters of toluene and washed with waterin a separate funnel. The lower water layer was discarded and the toptoluene layer was run through a silica plug. Then the solvent wasevaporated yielding a viscous very dark yellow dye. The spectralstrength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured in toluene as about 27,194mL*Absorbance Units per gram at absorption X.

EXAMPLE 8

The Coupling of Dimer Dianthranilate Bis-Diazo top-hydroxyethylanilino-acetoacetamide. A compound of the formula

was prepared as follows. Dissolving thep-hydroxyethylanilino-acetoacetamide. To a liter beaker with magneticstir bar was charged about 700 grams of deionized water, about 16.0grams of acetic acid, and about 22.2 grams of sodium hydroxide. Thecontents were stirred until completely dissolved. About 700 millilitersof isopropyl alcohol and about 12.1 grams ofp-hydroxyethylanilino-acetoacetamide from Example 4 above was then addedand stirred until dissolved.

Adding the Dimer Dianthranilate Bis-Diazo to the Dissolvedp-hydroxyethylanilino-acetoacetamide. The cooled contents from Example5, Part A above were added to the beaker containing thep-hydroxyethylanilino-acetoacetamide solution. A yellow precipitateformed at the beginning of coupling, and then the solids turned into avery viscous liquid. After stirring for about one hour, the contentswere allowed to settle over night. The top liquid was decanted. Thebottom viscous liquid contained white salt and yellow product. About 700milliliters of deionized water was added to the solids and stirred forabout one hour. The aqueous layer was then discarded. The bottom yellowviscous liquid product was dissolved in about 300 milliliters of tolueneand washed with water in a separatory funnel. The lower water layer wasdiscarded and the top toluene layer was run through a silica plug. Thenthe toluene was evaporated yielding a viscous very dark yellow dye. Thespectral strength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured as about 32,363 ml*AbsorbanceUnits per gram at absorption λ_(max).

EXAMPLE 9

Menthyl Anthranilate-Diazotization. To a 150 milliliter 3-neck roundbottom flask equipped with mechanical stirrer, salt/ice bath, andthermometer was charged about 11.9 grams of menthyl anthranilate(MW=275), about 29.7 grams of acetic acid, about 5.9 grams of water andabout 1.5 grams of concentrated H₂SO₄. The contents were stirred untildissolved while keeping the temperature of the ice bath at about 0° C.About 16.5 grams of nitrosyl sulfuric acid (NSA MW=127, 40% by weight)was added slowly through an addition funnel maintaining the reactiontemperature below about 3° C. The addition took about 32 minutes. Thecooled reaction mixture was stirred an additional two hours and a PMAtest was (to determine excess NO+) was run and the result was positiveindicating the reaction was complete. About 1.8 grams of sulfamic acidwas added (to react with excess NSA) and stirred for about 20 minutes. APMA test confirmed that all excess NSA had been killed. At this pointthe reaction mixture is ready to couple.

EXAMPLE 10

The Coupling of Menthyl Anthranilate Diazo to2-ethylhexylacetoacetamide. A compound of the formula

was prepared as follows. Dissolving the 2-ethylhexylacetoacetamide. To a1 liter beaker with magnetic stir bas was added about 100 grams ofwater, about 16 grams of acetic acid and about 22 grams of sodiumhydroxide and stirred until everything was dissolved. About 700milliliters of methanol was then added with stirring and the contentsremained clear. About 9.3 grams of the acetoacetamide from Example 1above was then added to the beaker. The solution remained clear. Afterstirring for several minutes the solution became cloudy About 120 gramsof additional water was added until the solution became clear again.

Adding the Menthyl Anthranilate Diazo to the Dissolved2-Ethylhexylacetoacetamide: The cooled contents from Example 9 abovewere then slowly added to this solution allowing the azo coupling totake place. A yellow solids immediately began to precipitate out ofsolution. After stirring for about one hour the solids turned to oilwith a lot of white salt. More water was added to the reaction contentsuntil the salts dissolved. The contents were allowed to stir overnight.The aqueous layer was decanted and the remaining deep yellow oil wasdissolved in toluene and washed with water in a separatory funnel. Thebottom water layer was discarded while the top toluene layer was runthrough a silica gel plug. The solvent was evaporated. The spectralstrength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured as about 44,517 ml*AbsorbanceUnits per gram at absorption λ_(max).

EXAMPLE 11

The Coupling of Menthyl Anthranilate Diazo to dodecylacetoacetamide. Acompound of the formula

was prepared as follows. Dissolving the dodecylanilinoacetoacetamide. Toa 1 liter beaker with magnetic stir bar was added about 100 g rams ofwater, about 16 grams of acetic acid and about 22 grams of sodiumhydroxide and stirred until everything was dissolved. About 700milliliters of isopropyl alcohol was added and the solution becamecloudy. An additional about 140 grams of water were added with stirringand the contents became clear. About 14.9 grams of the acetoacetamidefrom Example 2 above was then added to the beaker. The solution remainedclear.

Adding the Menthyl Anthranilate Diazo to the DissolvedDodecylanilino-acetoacetamide: The cooled contents from Example 9 abovewere then slowly added to this solution allowing the azo coupling totake place. An oily, gooey mass began to precipitate out of solution.The contents were allowed to stir overnight. The next day the water wasdecanted off and the gooey solid was dissolved in toluene andtransferred to a separatory funnel. The product dissolved in toluene waswashed with water, separated, and the toluene layer run through a silicaplug. The solvent was evaporated leaving a viscous oily yellow product.The spectral strength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured as about 37,949 ml*AbsorbanceUnits per gram at absorption λ_(max).

EXAMPLE 12

An ink base was prepared by melting, admixing, and filtering thefollowing ingredients: 43.59 parts by weight polyethylene wax (PE 6550,obtained from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃); 19.08parts by weight stearyl stearamide wax (KEMAMIDE®0 S-180, obtained fromCrompton Corporation); 18.94 parts by weight tetra-amide resin obtainedfrom the reaction or one equivalent of a C-36 dimer acid (obtained fromUniqema, New Castle, Del.) with two equivalents of ethylene diamine andUNICID® 700 (obtained from Baker Petrolite), a long chain hydrocarbonhaving a terminal carboxylic acid group, prepared as described inExample 1 of U.S. Pat. No. 6,174,937, which is hereby incorporated byreference herein in its entirety 11.71 parts by weight urethane resinobtained from the reaction of two equivalents of ABITOL® E hydroabietylalcohol (obtained from Hercules Inc.) and one equivalent of isophoronediisocyanate, prepared as described in Example 1 of U.S. Pat. No.5,782,966, which is hereby incorporated by reference herein; 6.48 partsby weight urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol, prepared as describedin Example 4 of U.S. Pat. No. 6,309,453, which is hereby incorporated byreference herein in its entirety; and 0.20 parts by weight. NAUGUARD®445 antioxidant (obtained from Uniroyal Chemical Co.).

Thereafter, 600 grams of the ink carrier components as listed above inthe percentages as listed above were added to a 1 liter beaker andheated in an oven at 135° C. until molten. Subsequently, the beaker wasinserted into a heating mantle set to 135° C. and the contents of thebeaker were stirred for 45 minutes. The resulting ink was then filteredthrough a combination of Whatman #3 and 0.2 micron NAE filters andplaced in a Mott filter assembly. Filtration was supported by theaddition of 1 percent by weight. FILTER-AID obtained from Fluka Chemika,and proceeded at a temperature of 135° C. until complete after 6 hours.The ink base was poured into molds containing about 31 grams of thecolorless ink base and allowed to cool.

EXAMPLE 13

Preparation of Ink Containing Colorant. About 29.9 grams of ink basefrom Example 12 was placed in a 100 milliliter beaker with a magneticstir bar and subsequently placed in a 135° C. oil bath until molten.About 2.0 grams of the product of Example 6 above was then added andstirred for about 3 hours. The yellow colored ink was then poured intoan aluminum mold.

EXAMPLE 14

Printing of Ink Samples Containing Colorant. Printed samples of the inkprepared in Example 13 were generated on HAMMERMILL LASERPRINT® paperusing a K Printing Proofer (manufactured by RK Print Coat InstrumentLtd., Litlington, Royston, Heris, SG8 0OZ, U.K.). In this method, thetested inks were melted onto a printing plate set at 150° C.temperature. A roller bar fitted with the paper was then rolled over theplate containing the melted ink on its surface, The ink on the paper wascooled, resulting in three separated images of rectangular blocks. Themost intensely colored block contained the most ink deposited on thepaper, and was therefore used to obtain the color value measurements.The printed samples were evaluated visually.

It will be appreciated that various of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications Also thatvarious presently unforeseen or unanticipated alternatives,modifications, variations or improvements therein may be subsequentlymade by those skilled in the art which are also intended to beencompassed by the following claims. Unless specifically recited in aclaim, steps or components of claims should not be implied or importedfrom the specification or any other claims as to any particular order,number, position, size, shape, angle, color, or material.

1. A phase change ink composition comprising a phase change ink carrierand a compound of the formula

wherein R and R′, if R′ is present, is an N-substituted acetoacetamide,wherein R₂ is (i) an alkyl group, including substituted andunsubstituted alkyl groups, and wherein hereto atoms either may or maynot be present in the alkyl group, (ii) an alkylene group, includingsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (iii) an arylenegroup, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup (iv) an arylalkylene group, including substituted andunsubstituted arylalkylene groups, and wherein hetero atoms either mayor may not be present in the arylalkylene group, (v) an alkylarylenegroup including substituted and unsubstituted alkylarylene groups, andwherein hetero atoms either may or may not be present in thealkylarylene group, (vi) an alkyleneoxy group, including substituted andunsubstituted alkyleneoxy groups, and wherein hetero atoms either may ormay not be present in the alkyleneoxy group, (vii) an aryleneoxy group,including substituted and unsubstituted aryleneoxy groups, and whereinhetero atoms either may or may not be present in the aryleneoxy group,(viii) an arylalkyleneoxy group, including substituted and unsubstitutedarylalkyleneoxy groups, and wherein hereto atoms either may or may notbe present in the arylalkyleneoxy group, (ix) an alkylaryleneoxy group,including substituted and unsubstituted alkylaryleneoxy groups, andwherein hetero atoms either may or may not be present in thealkylaryleneoxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a heterocyclic group, (xv) a silylenegroup, (xvi) a siloxane group, (xvii) a polysilylene group, or (xviii) apolysiloxane group; wherein X and X′, if X′ is present, is a (i) directbond, (ii) an oxygen atom, (iii) a nitrogen atom, (iv) a sulfur atom,(v) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom, analkyl group, including substituted and unsubstituted alkyl groups, andwherein hetero atoms either may or may not be present in the alkylgroup, an aryl group, including substituted and unsubstituted arylgroups, and wherein hetero atoms either may or may not be present in thearyl group, an arylalkyl group, including substituted and unsubstitutedarylalkyl groups, and wherein hetero atoms either may or may not bepresent in the arylalkyl group, or an alkylaryl group, includingsubstituted and unsubstituted alkylaryl groups, and wherein hetero atomseither may or may not be present in the alkylaryl group, (vi) or a groupof the formula —CR₅₀R₆₀—; wherein R₅₀ and R₆₀ each, independently of theother, is a hydrogen atom, an alkyl group, including substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group, an aryl group, including substitutedand unsubstituted aryl groups, and wherein hetero atoms either may ormay not be present in the aryl group an arylalkyl group, includingsubstituted and unsubstituted arylalkyl groups, and wherein hetero atomseither may or may not be present in the arylalkyl group, or an alkylarylgroup, including substituted and unsubstituted alkylaryl groups, andwherein hetero atoms either may or may not be present in the alkylarylgroup, wherein two or more substituents can be joined together to form aring, and wherein X and X′ can be the same as each other or differentfrom each other; wherein Z and Z′ are each optionally present and ifpresent are each independently selected from a (i) hydrogen atom, (ii) ahalogen atom, (iii) a nitro group, (iv) an alkyl group, includingsubstituted and unsubstituted alkyl groups, and wherein hetero atomseither may or may not be present in the alkyl group, (v) an aryl group,including substituted and unsubstituted aryl groups, and wherein heteroatoms either may or may not be present in the aryl group, (vi) anarylalkyl group, including substituted and unsubstituted arylalkylgroups, and wherein hetero atoms either may or may not be present in thearylalkyl group, (vii) an alkylaryl group, including substituted andunsubstituted alkylaryl groups, and wherein hetero atoms either may ormay not be present in the alkylaryl group, (viii) a group of the formula

wherein R₇₀ is an alkyl group, including substituted and unsubstitutedalkyl groups, and wherein hetero atoms either may or may not be presentin the alkyl group, an aryl group, including substituted andunsubstituted aryl groups, and wherein hetero atoms either may or maynot be present in the aryl groups, an arylalkyl group, includingsubstituted and unsubstituted arylalkyl groups, and wherein hetero atomseither may or may not be present in the arylalkyl group, an alkylarylgroup, including substituted and unsubstituted alkylaryl groups, andwherein hetero atoms either may or may not be present in the alkylarylgroup, an alkoxy group, including substituted and unsubstituted alkoxygroups, and wherein hetero atoms either may or may not be present in thealkoxy group, an aryloxy group, including substituted and unsubstitutedaryloxy groups, and wherein hetero atoms either may or may not bepresent in the aryloxy group, an arylalkyloxy group, includingsubstituted and unsubstituted arylalkyloxy groups, and wherein heteroatoms either may or may not be present in the arylalkyloxy group, analkylaryloxy group, including substituted and unsubstituted alkylaryloxygroups, and wherein hetero atoms either may or may not be present in thealkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, aheterocyclic group, a silyl group, a siloxane group, a polysilylenegroup, or a polysiloxane group, (ix) a sulfonyl group of the formula—SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, includingsubstituted and unsubstituted alkyl groups, and wherein hetero atomseither may or may not be present in the alkyl group, an aryl group,including substituted and unsubstituted aryl groups, and wherein heteroatoms either may or may not be present in the aryl group, an arylalkylgroup, including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms either may or may not be present in the arylalkylgroup, an alkylaryl group, including substituted and unsubstitutedalkylaryl groups, and wherein hetero atoms either may or may not bepresent in the alkylaryl group, an alkoxy group, including substitutedand unsubstituted alkoxy groups, and wherein hetero atoms either may ormay not be present in the alkoxy group, an aryloxy group, includingsubstituted and unsubstituted aryloxy groups, and wherein hetero atomseither may or may not be present in the aryloxy group, an arylalkyloxygroup, including substituted and unsubstituted arylalkyloxy groups, andwherein hetero atoms either may or may not be present in thearylalkyloxy group, an alkylaryloxy group, including substituted andunsubstituted alkylaryloxy groups, and wherein hetero atoms either mayor may not be present in the alkylaryloxy group, a polyalkyleneoxygroup, a polyaryleneoxy group, a polyarylalkyleneoxy group, apolyalkylaryleneoxy group, a heterocyclic group, a silyl group, asiloxane group, a polysilylene group, or a polysiloxane group, or (x) aphosphoryl group or the formula —PO₃R₉₀ wherein R₉₀ is a hydrogen atom,an alkyl group, including substituted and unsubstituted alkyl groups andwherein hetero atoms either may or may not be present in the alkylgroup, an aryl group, including substituted and unsubstituted arylgroups, and wherein hetero atoms either may or may not be present in thearyl group, an arylalkyl group, including substituted and unsubstitutedarylalkyl groups, and wherein hetero atoms either may or may not bepresent in the arylalkyl group, an alkylaryl group, includingsubstituted and unsubstituted alkylaryl groups, and wherein hetero atomseither may or may not be present in the alkylaryl group, an alkoxygroup, including substituted and unsubstituted alkoxy groups, andwherein hetero atoms either may or may not be present in the alkoxygroup, an aryloxy group, including substituted and unsubstituted aryloxygroups, and wherein hetero atoms either may or may not be present in thearyloxy group, an arylalkyloxy group, including substituted andunsubstituted arylalkyloxy groups, and wherein hetero atoms either mayor may not be present in the arylalkyloxy group, an alkylaryloxy group,including substituted and unsubstituted alkylaryloxy groups, and whereinhetero atoms either may or may not be present in the alkylaryloxy group,a polyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxygroup, a polyalkylaryleneoxy group, a heterocyclic group, a silyl group,a siloxane group, a polysilylene group, or a polysiloxane group, whereintwo or more substituents can be joined together to form a ring, andwherein Z and Z′ can be the same as each other or different from eachother; and wherein Z and X can be joined together to form a ring andwherein Z′ and X′ can be joined together to form a ring.
 2. A phasechange ink composition according to claim 1 wherein the phase change inkcarrier comprises a monoamide, a tetraamide, or a mixture thereof.
 3. Aphase change ink composition according to claim 1 wherein the phasechange ink carrier comprises (a) stearyl stearamide, (b) a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and stearic acid, or (c) mixtures thereof.
 4. A phase changeink composition according to claim 1 wherein the phase change inkcarrier comprises (a) stearyl stearamide, (b) a dimer acid basedtetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms, or(c) mixtures thereof.
 5. A phase change ink composition according toclaim 1 wherein the phase change ink carrier comprises anisocyanate-derived material, a urethane isocyanate-derived material, aurea isocyanate-derived material, a urethane/urea isocyanate-derivedmaterial, or mixtures thereof.
 6. A phase change ink compositionaccording to claim 1 wherein the phase change ink carrier comprises amixture of one or more amides and one or more isocyanate-derivedmaterials.
 7. A phase change ink composition according to claim 1wherein the phase change ink carrier comprises one or more materialsselected from paraffins, microcrystalline waxes, polyethylene waxes,ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides,sulfonamide materials, tall oil rosins, rosin esters, ethylene/vinylacetate copolymers, ethylene/acrylic acid copolymers, ethylene/vinylacetate/acrylic acid copolymers, copolymers of acrylic acid withpolyamides, ionomers, and mixtures thereof.
 8. A phase change inkcomposition according to claim 1 wherein the phase change ink carrier ispresent in the ink in an amount of at least about 0.1 percent by weightof the ink and wherein the phase change ink carrier is present in theink in an amount of no more than about 99 percent by weight of the ink.9. A phase change ink composition according to claim 1 wherein the inkfurther contains an antioxidant.
 10. A phase change ink compositionaccording to claim 1 wherein the ink further contains a viscositymodifier.
 11. A phase change ink composition according to claim 1wherein the ink carrier comprises (a) a polyethylene wax in an amount ofat least about 25 percent by weight of the ink and in an amount of nomore than about 60 percent by weight of the ink, (b) a stearylstearamide wax in an amount of at least about 8 percent by weight of theink and in an amount of no more than about 32 percent by weight of theink, (c) a dimer acid based tetra-amide that is the reaction product ofdimer acid, ethylene diamine, and a carboxylic acid having at leastabout 36 carbon atoms in an amount of at least about 10 percent byweight of the ink and in an amount of no more than about 32 percent byweight of the ink, (d) a urethane resin derived from the reaction of twoequivalents of hydroabietyl alcohol and one equivalent of isophoronediisocyanate in an amount of at least about 6 percent by weight of theink and in an amount of no more than about 16 percent by weight of theink, (e) a urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol in an amount of at leastabout 2 percent by weight of the ink and in an amount of no more thanabout 13 percent by weight of the ink, and (f) an antioxidant in anamount of at least about 0.01 percent by weight of the ink and in anamount of no more than about 1 percent by weight of the ink.
 12. A phasechange ink composition according to claim 1, wherein the colorant ispresent in the ink in an amount of at least about 1 percent by weight ofthe ink.
 13. A phase change ink composition according to claim 1,wherein the colorant is present in the ink in an amount of no more thanabout 20 percent by weight of the ink.
 14. A phase change inkcomposition according to claim 1, wherein the ink has a melting point ofno lower than about 50° C. and wherein the ink has a melting point of nohigher than about 160° C.
 15. A phase change ink composition accordingto claim 1, wherein the ink has a melt viscosity at a temperature ofabout 140° C. of no more than about 30 centipoise.
 16. A phase changeink composition according to claim 1, wherein the ink has a meltviscosity at a temperature of about 140° C. of no less than about 1centipoise.
 17. A phase change ink composition according to claim 1,wherein R and R′, if R′ is present, is 2-ethylhexylacetoacetamide,dodecylanilineacetoacetamide, Guerbet-acetoacetamide, orp-hydroxyethylanilino-acetoacetamide.
 18. A phase change ink compositionaccording to claim 1, wherein R₂ is a linear alkylene group.
 19. A phasechange ink composition according to claim 1, wherein R₂ is a branchedalkylene group.
 20. A phase change ink composition according to claim 1wherein R₂ is a saturated alkylene group.
 21. A phase change inkcomposition according to claim 1, wherein R₂ is an unsaturated alkylenegroup.
 22. A phase change ink composition according to claim 1, whereinR₂ is an unsubstituted alkylene group.
 23. A phase change inkcomposition according to claim 1, wherein R₂ is a substituted alkylenegroup.
 24. A phase change ink composition according to claim 1, whereinR₂ is an alkylene group with at least about 10 carbon atoms.
 25. A phasechange ink composition according to claim 1, wherein R₂ is an alkylenegroup with about 36 carbon atoms.
 26. A phase change ink compositionaccording to claim 1, wherein R₂ is


27. A phase change ink composition according to claim 1, wherein R₂ is abranched alkylene group having 36 carbon atoms which may includeunsaturations and cyclic groups.
 28. A phase change ink compositionaccording to claim 1, wherein the colorant compound is of the formula


29. A phase change ink composition according to claim 1, wherein thecolorant compound is of the formula


30. A phase change ink composition according to claim 1 wherein thecolorant compound is of the formula


31. A phase change ink composition according to claim 1, wherein thecolorant compound is of the formula


32. A phase change ink composition according to claim 1, wherein thecolorant compound is of the formula


33. A phase change ink composition according to claim 1, wherein thecolorant compound is of the formula


34. A phase change ink composition according to claim 1, wherein thecolorant compound is of the formula


35. A phase change ink composition according to claim 1, wherein thecolorant compound is of the formula


36. A process which comprises (1) incorporating into an ink jet printingapparatus a phase change ink composition comprising a phase change inkcarrier and a colorant compound of the formula

wherein R and R′, if R′ is present, is an N-substituted acetoacetamide;wherein R₂ is (i) an alkyl group, including substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group, (ii) an alkylene group, includingsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (iii) an arylenegroup, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup (iv) an arylalkylene groups including substituted andunsubstituted arylalkylene groups, and wherein hetero atoms either mayor may not be present in the arylalkylene group, (v) an alkylarylenegroup, including substituted and unsubstituted alkylarylene groups, andwherein hetero atoms either may or may not be present in thealkylarylene group, (vi) an alkyleneoxy group, including substituted andunsubstituted alkyleneoxy groups, and wherein hetero atoms either may ormay not be present in the alkyleneoxy group, (vii) an aryleneoxy group,including substituted and unsubstituted aryleneoxy groups, and whereinhetero atoms either may or may not be present in the aryleneoxy group,(viii) an arylalkyleneoxy group, including substituted and unsubstitutedarylalkyleneoxy groups, and wherein hetero atoms either may or may notbe present in the arylalkyleneoxy group, (ix) an alkylaryleneoxy group,including substituted and unsubstituted alkylaryleneoxy groups, andwherein hetero atoms either may or may not be present in thealkylaryleneoxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a heterocyclic group, (xv) a silylenegroup, (xvi) a siloxane group, (xvii) a polysilylene group, or (xviii) apolysiloxane group; wherein X and X′, if X′ is present, is a (i) directbond, (ii) an oxygen atom, (iii) a nitrogen atom, (iv) a sulfur atom,(v) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,(vi) or a group of the formula CR₅₀R₆₀—; wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, wherein two or moresubstituents can be joined together to form a ring, and wherein X and X′can be the same as each other or different from each other; wherein Zand Z′ are each optionally present and if present are each independentlyselected from a (i) hydrogen atom, (ii) a halogen atom, (iii) a nitrogroup, (iv) an alkyl group, (v) an aryl group, (vi) an arylalkyl group,(vii) an alkylaryl group, (viii) a group of the formula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, an alkoxy group, an aryloxy group, an arylalkyloxygroup, an alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxygroup, a heterocyclic group, a silyl group, a siloxane group, apolysilylene group, or a polysiloxane group, (ix) a sulfonyl group ofthe formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, anaryl group, an arylalkyl group, an alkylaryl group, an alkoxy group, anaryloxy group, an arylalkyloxy group, an alkylaryloxy group, apolyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxygroup, a polyalkyaryleneoxy group, a heterocyclic group, a silyl group,a siloxane group, a polysilylene group, or a polysiloxane group, or (x)a phosphoryl group of the formula —PO₃R₉₀ wherein R₉₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, an alkylarylgroup, an alkoxy group, an aryloxy group, an arylalkyloxy group, analkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, apolyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclicgroup, a silyl group, a siloxane group, a polysilylene group, or apolysiloxane group, wherein two or more substituents can be joinedtogether to form a ring, and wherein Z and Z′ can be the same as eachother or different from each other; and wherein Z and X can be joinedtogether to form a ring and wherein Z′ and X′ can be joined together toform a ring; (2) melting the ink; and (3) causing droplets of the meltedink to be ejected in an imagewise pattern onto a substrate.
 37. Aprocess according to claim 36, wherein the printing apparatus employs apiezoelectric printing process wherein droplets of the ink are caused tobe ejected in imagewise pattern by oscillations of piezoelectricvibrating elements.
 38. A process according to claim 36, wherein thesubstrate is a final recording sheet and droplets of the melted ink areejected in an imagewise pattern directly onto the final recording sheet.39. A process according to claim 36, wherein the substrate is anintermediate transfer member and droplets of the melted ink are ejectedin an imagewise pattern onto the intermediate transfer member followedby transfer of the imagewise pattern from the intermediate transfermember to a final recording sheet.
 40. A process according to claim 36,wherein the intermediate transfer member is heated to a temperatureabove that of the final recording sheet and below that of the melted inkin the printing apparatus.